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WO1998014416A1 - Compositions et methodes inhibant la polymerisation de monomeres aromatiques vinyliques - Google Patents

Compositions et methodes inhibant la polymerisation de monomeres aromatiques vinyliques Download PDF

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Publication number
WO1998014416A1
WO1998014416A1 PCT/US1997/016292 US9716292W WO9814416A1 WO 1998014416 A1 WO1998014416 A1 WO 1998014416A1 US 9716292 W US9716292 W US 9716292W WO 9814416 A1 WO9814416 A1 WO 9814416A1
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WO
WIPO (PCT)
Prior art keywords
composition
vinyl aromatic
monomer
formula
polymerization
Prior art date
Application number
PCT/US1997/016292
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English (en)
Inventor
Graciela B. Arhancet
Original Assignee
Betzdearborn Inc.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Betzdearborn Inc. filed Critical Betzdearborn Inc.
Publication of WO1998014416A1 publication Critical patent/WO1998014416A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C7/00—Purification; Separation; Use of additives
    • C07C7/20—Use of additives, e.g. for stabilisation

Definitions

  • the present invention relates to compositions and methods for inhibiting the polymerization of vinyl aromatic monomer compounds.
  • styrene Common industrial methods for producing styrene typically include separation and purification processes such as distillation to remove unwanted impurities. Unfortunately, purification processes carried out at elevated temperatures result in an increased rate of undesired polymeri- zation. Distillation is generally carried out under vacuum to minimize loss of monomer. The presence of oxygen, which is typically excluded from styrene distillation, will also promote polymerization of the monomer. This polymerization results not only in loss of desired monomer end-product, but also in the uses of production efficiency caused by polymer formation and/or agglomeration of polymer on process equipment. Thermal polymerization, which typically occurs during distillation, of styrene monomer results in the formation of normal (i.e., linear) polymer. This resulting polystyrene polymer is characterized by its glassy and transparent appearance and its solubility in the styrene monomer and many organic solvents.
  • the compounds generally used commercially to inhibit polymerization of vinyl aromatic monomers are of the dinitrophenol family.
  • U.S. Pat. No. 4,105,506, Watson et al. teaches the use of 2,6-di- nitro-p-cresol as a polymerization inhibitor for vinyl aromatic compounds.
  • U.S. Pat. No. 4,466,905 Butler et al. teaches that a combination of 2,6- dinitro-p-cresol and p-phenylenediamine will inhibit polymerization in a distillation column when oxygen is present.
  • U.S. Pat. No. 4,774,374, Abruscato et al. teaches compositions for inhibiting the polymerization of vinyl aromatic compounds.
  • composition is an oxygenated product of the reaction of N-aryl-N'-alkyl-p-phenylenediamine with oxygen.
  • U.S. Pat. Nos. 5,426,257 and 5,489,718, Arhancet teach methods and compositions for inhibiting the polymerization of vinyl aromatic monomers comprising an oxime compound and a hydroxylamine compound and/or a phenylenedia- mine.
  • U.S. Pat. No. 5,254,760, Winter et al. teaches compositions and processes for inhibiting vinyl aromatic compound polymerization. The processes comprise adding to the vinyl aromatic compounds during purification or distillation a mixture of a stable hindered nitroxyl compound and an aromatic nitro compound.
  • U.S. Pat. No. 4,670,131 , Ferrell teaches methods for inhibiting fouling of hydrocarbons containing unsaturated compounds with a stable free radical.
  • the stable free radical can be a nitroxide compound.
  • inhibitor compositions have been employed in styrene and other vinyl aromatic monomers to inhibit undesired polymerization.
  • Agents that have been used include sulfur, p-benzoquinone, tert-butyl pyrocatechol, phenothiazine, and hindered phenols.
  • many of these compounds present disadvantages such as high intoxicity, instability, explosive hazard at elevated temperature and insufficient efficacy under processing conditions (i.e., inhibitor requires oxygen to be effective).
  • the present inventor has discovered a novel composition which acts to inhibit vinyl aromatic monomer polymerization while avoiding the problems of certain known inhibitors.
  • the present invention relates to compositions and methods for in- hibiting the polymerization of vinyl aromatic monomer compounds comprising adding to the monomers a combination of a stable hindered nitroxyl radical and an oxime compound.
  • compositions of the present invention are effective at inhibiting polymerization of vinyl aromatic monomers under processing conditions. These processing conditions include but are not limited to preparation, purification, distillation and vacuum distillation processes.
  • the compositions of the present invention are effective in both processes where oxygen is present and under oxygen-free conditions.
  • oxygen-free is meant to define the substantially oxygen free conditions under which vinyl aromatic monomers, particularly styrene, are often processed. These conditions, exemplified by distillation and purification processes generally have less than 2 parts per million parts of oxygen present and preferably less than 1 part of oxygen per million parts styrene.
  • the vinyl aromatic monomers that are treated by the compositions of the present invention include but are not limited to styrene, bromosty- rene, divinylbenzene, and ⁇ -methylstyrene.
  • the compositions of the present invention are particularly efficacious at inhibiting the polymerization of styrene monomer.
  • the stable hindered nitroxyl radical generally has the formula:
  • R is a Ci to C 3 alkyl group; or a cyclic compound having the formula:
  • R" is a C2 to C17 alkyl group; benzoate, phthalate, terephthalate, sebacate, succinate, and adipate.
  • the oxime compounds generally have the formula:
  • R 2 and R 3 are the same or different and are hydrogen, alkyl, aryl, alkaryl, aralkyl, alkylhydroxyaryl or arylhydroxyalkyl groups having three to about twenty carbon atoms.
  • examples of these compounds include but are not limited salicylaldoxime and 5-nonylsalicylaldoxime.
  • the total amount of stable hindered nitroxyl radical and oxime compound used in the methods of the present invention is that amount which is sufficient to inhibit polymerization and will vary according to the conditions under which the vinyl aromatic monomer is being processed, and the temperature of the system. At higher processing temperatures and higher monomer contamination, larger amounts of the polymerization inhibiting composition are generally required.
  • Styrene for example, is typically processed at temperatures between 95° and 125°C.
  • the compositions of the present invention are effective at inhibiting the polymerization of styrene over this range of temperatures.
  • the term "effective inhibiting amount" is defined as that amount which is effective at inhibiting polymerization.
  • the effective amount ranges from about 1 part to about 10,000 parts per million parts of monomer. More preferably, the effective amount ranges from about 1 part to about 1000 parts per million parts of monomer.
  • the weight ratio of the stable hindered nitroxyl radical to oxime compound will generally range from about 9:1 to about 1 :9 with a weight ratio of about 1 : 1 preferred.
  • compositions of the present invention can be added to the vinyl aromatic monomer by any conventional method at any point of the processing system, either as separate and individual ingredients or as a combination of ingredients.
  • compositions of the present invention may be added to the vinyl aromatic monomer as either a dispersion or as a solution using a suitable liquid carrier or solvent. Any solvent that is compatible with the individual ingredients of the composition and the vinyl aromatic monomer to be treated may be employed.
  • Example 1 5 mL of uninhibited styrene was placed in a test tube and the appropriate amount of treatment was added. The tube was capped with a rubber septum and argon was bubbled through the liquid at 10 mL/min for 3 minutes. The tubes utilized in Example 1 where then placed in an oil bath heated to 110°C for 2 hours. The amount of polystyrene formed was determined by methanol precipitation. The results of this testing are presented in Table I.
  • TEMPO 2,2,6,6-tetramethyl-l-piperidinoxy
  • free radical tAtBN is tert-amyl-tert-butyl aminoxyl
  • free radical OHTEMPO is 4-hydroxy-2,2,6,6-tetramethyl-1-piperidinoxy
  • free radical SA is salicylaldoxime
  • NSA is 5-nonylsalicylaldoxime
  • Example 2 The procedure of Example 1 was repeated using an oil bath heated at 120°C. The results of Example 2 are reported in Table II.
  • TEMPO 300 3.49 tAtBN 600 0.44 tAtBN/SA 400/200 0.75 tAtBN/SA 300/300 0.53 tAtBN/SA 200/400 1.03 tAtBN 600 0.95
  • uninhibited styrene 100 mL was placed in a 250 mL three-necked flask fitted with a bubbler, a septa, and a condenser.
  • 200 ppm of TEMPO and 200 ppm of SA were added and argon was bubbled through the solution at 10 mL/min for 10 minutes. While argon sparging continued, the flask was immersed in an oil bath heated at 110°C. 5.0 mL samples were taken every 30 minutes and the amount of polymer formed was determined by methanol precipitation. After heating for three hours, polymer content was 0.04%.
  • Example 4 the procedure of Example 3 was followed except
  • Example 5 Another study was performed demonstrating that the inventive composition provided better results than the individual stable hindered nitroxyl radical.
  • Example 5 the procedure of Example 3 was followed except samples were taken every hour. The results of this testing are presented in Table III.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Analytical Chemistry (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Water Supply & Treatment (AREA)
  • Polymerisation Methods In General (AREA)

Abstract

La polymérisation de monomères aromatiques vinyliques tels que le styrène peut être inhibée par l'adjonction d'un radical nitroxyle stable entravé et d'un composé d'oxime.
PCT/US1997/016292 1996-10-04 1997-09-16 Compositions et methodes inhibant la polymerisation de monomeres aromatiques vinyliques WO1998014416A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US72088596A 1996-10-04 1996-10-04
US08/720,885 1996-10-04

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WO1998014416A1 true WO1998014416A1 (fr) 1998-04-09

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Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2000017241A1 (fr) * 1998-09-17 2000-03-30 Loctite (R & D) Limited Systemes d'auto-oxidation pour compositions polymerisables activables par l'air
WO2000039209A1 (fr) * 1998-12-23 2000-07-06 Ciba Specialty Chemicals Holding Inc. Stabilisants polymeres presentant une polydispersite faible
US6300533B1 (en) 1999-08-16 2001-10-09 Uniroyal Chemical Company, Inc. Inhibition of polymerization of ethylenically unsaturated monomers
US6344560B1 (en) 2000-05-03 2002-02-05 Uniroyal Chemical Company, Inc. Nitroaromatic solubilizer for nitroxyls in aromatic solvents
US6403850B1 (en) 2000-01-18 2002-06-11 Uniroyal Chemical Company, Inc. Inhibition of polymerization of unsaturated monomers
US6653414B2 (en) 1999-12-02 2003-11-25 Uniroyal Chemical Company, Inc. Inhibition of polymerization of unsaturated monomers
US6660181B2 (en) 1999-12-02 2003-12-09 Crompton Corporation Inhibition of polymerization of unsaturated monomers
US6685823B2 (en) 2000-10-16 2004-02-03 Uniroyal Chemical Company, Inc. C-nitrosoaniline compounds and their blends as polymerization inhibitors
WO2005070989A2 (fr) * 2004-01-27 2005-08-04 Ciba Specialty Chemicals Holding Inc. Compositions photodurcissables cationiques thermiquement stables
US7045647B2 (en) 2000-10-16 2006-05-16 Uniroyal Chemical Company, Inc. Blends of quinone alkide and nitroxyl compounds and polymerization inhibitors
US7553896B2 (en) 2005-06-17 2009-06-30 Chemtura Corporation Ortho-nitrosophenols as polymerization inhibitors
US7943809B2 (en) 1999-12-03 2011-05-17 Chemtura Corporation Composition and method for inhibiting polymerization and polymer growth
US8110650B2 (en) 2006-12-22 2012-02-07 Reichold, Inc. Methods for making molding resins
US8691994B2 (en) 2011-02-03 2014-04-08 Nalco Company Multi-component polymerization inhibitors for ethylenically unsaturated monomers
EP2516409B1 (fr) * 2009-12-21 2017-01-25 Blue Cube IP LLC Procédé d'élaboration de dioxydes de divinylarène

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4237326A (en) * 1979-05-30 1980-12-02 Mitsubishi Petrochemical Company Limited Method of inhibiting polymerization of styrene
US5489718A (en) * 1994-06-30 1996-02-06 Betz Laboratories, Inc. Compositions and methods for inhibiting vinyl aromatic monomer polymerization
US5545786A (en) * 1994-11-28 1996-08-13 Ciba-Geigy Corporation Method for inhibiting premature polymerization of vinyl aromatic monomers
US5583247A (en) * 1995-04-14 1996-12-10 Ciba-Geigy Corporation 7-substituted quinone methides as inhibitors for unsaturated monomers

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4237326A (en) * 1979-05-30 1980-12-02 Mitsubishi Petrochemical Company Limited Method of inhibiting polymerization of styrene
US5489718A (en) * 1994-06-30 1996-02-06 Betz Laboratories, Inc. Compositions and methods for inhibiting vinyl aromatic monomer polymerization
US5545786A (en) * 1994-11-28 1996-08-13 Ciba-Geigy Corporation Method for inhibiting premature polymerization of vinyl aromatic monomers
US5545786C1 (en) * 1994-11-28 2001-10-16 Ciba Geigy Corp Method for inhibiting premature polymerization of vinyl aromatic monomers
US5583247A (en) * 1995-04-14 1996-12-10 Ciba-Geigy Corporation 7-substituted quinone methides as inhibitors for unsaturated monomers

Cited By (22)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2000017241A1 (fr) * 1998-09-17 2000-03-30 Loctite (R & D) Limited Systemes d'auto-oxidation pour compositions polymerisables activables par l'air
US6552140B1 (en) 1998-09-17 2003-04-22 Loctite (R&D) Limited Auto-oxidation systems for air-activatable polymerisable compositions
WO2000039209A1 (fr) * 1998-12-23 2000-07-06 Ciba Specialty Chemicals Holding Inc. Stabilisants polymeres presentant une polydispersite faible
US6583245B1 (en) 1998-12-23 2003-06-24 Ciba Specialty Chemicals Corporation Polymeric stabilizers having low polydispersity
US6300533B1 (en) 1999-08-16 2001-10-09 Uniroyal Chemical Company, Inc. Inhibition of polymerization of ethylenically unsaturated monomers
US6653414B2 (en) 1999-12-02 2003-11-25 Uniroyal Chemical Company, Inc. Inhibition of polymerization of unsaturated monomers
US6660181B2 (en) 1999-12-02 2003-12-09 Crompton Corporation Inhibition of polymerization of unsaturated monomers
US7943809B2 (en) 1999-12-03 2011-05-17 Chemtura Corporation Composition and method for inhibiting polymerization and polymer growth
US6403850B1 (en) 2000-01-18 2002-06-11 Uniroyal Chemical Company, Inc. Inhibition of polymerization of unsaturated monomers
US6344560B1 (en) 2000-05-03 2002-02-05 Uniroyal Chemical Company, Inc. Nitroaromatic solubilizer for nitroxyls in aromatic solvents
US6899806B2 (en) 2000-10-16 2005-05-31 Uniroyal Chemical Company, Inc. C-nitrosoaniline compounds and their blends as polymerization inhibitors
US6902663B2 (en) 2000-10-16 2005-06-07 Uniroyal Chemical Company, Inc. C-nitrosoaniline compounds and their blends as polymerization inhibitors
US7022220B2 (en) 2000-10-16 2006-04-04 Uniroyal Chemical Company, Inc. C-nitrosoaniline compounds and their blends as polymerization inhibitors
US7045647B2 (en) 2000-10-16 2006-05-16 Uniroyal Chemical Company, Inc. Blends of quinone alkide and nitroxyl compounds and polymerization inhibitors
US7473795B2 (en) 2000-10-16 2009-01-06 Uniroyal Chemical Company, Inc. Blends of quinone alkide and nitroxyl compounds as polymerization inhibitors
US6685823B2 (en) 2000-10-16 2004-02-03 Uniroyal Chemical Company, Inc. C-nitrosoaniline compounds and their blends as polymerization inhibitors
WO2005070989A2 (fr) * 2004-01-27 2005-08-04 Ciba Specialty Chemicals Holding Inc. Compositions photodurcissables cationiques thermiquement stables
WO2005070989A3 (fr) * 2004-01-27 2005-12-01 Ciba Sc Holding Ag Compositions photodurcissables cationiques thermiquement stables
US7553896B2 (en) 2005-06-17 2009-06-30 Chemtura Corporation Ortho-nitrosophenols as polymerization inhibitors
US8110650B2 (en) 2006-12-22 2012-02-07 Reichold, Inc. Methods for making molding resins
EP2516409B1 (fr) * 2009-12-21 2017-01-25 Blue Cube IP LLC Procédé d'élaboration de dioxydes de divinylarène
US8691994B2 (en) 2011-02-03 2014-04-08 Nalco Company Multi-component polymerization inhibitors for ethylenically unsaturated monomers

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